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MANUFAGTURB OP 'PYROXYL'INB COMPOUNDS. Y No. 393,751. Patented Dec. 4., 1 888.

N. Pains, Pham-magma wammgon. bfc.

UNITED STATES PATENT OFFICE.

JOSEPH E. FRANCE, OE NEW YORK, N.' Y.

MANUFACTURE OF PYROXYLINE COMPOUNDS.

lS151?..CIFICAJJJION forming part of Letters Patent No. 393,751, dated December 4, 1888.

Application filed January 5, 1888. Serial No. 259,849. (No specimens.)

To all whom it may concern:

Be it known that I, JOSEPH R. FRANCE, a citizen Of the United States, residing at New York, in the county of New York and State of New York, have invented new and useful Improvements in Manufacture of Pyroxyline Compounds, of which the following is a specication.

My invention relates to the manufacture of pyroxyline compounds; and the purpose thereof is to provide a novel method of treatment whereby the pulp may be properly dehydrated without danger of explosion, with economy to the manufacturer, and in quantities adapted to the daily requirements of the factory. In the manipulation of nitro-cellulose, preparatory to its treatment by solvents and following the nitration of the pulp and its subsequent washing, it is necessary to free it from the considerable body of water absorbed or adherent thereto before it can be converted into celluloid.

It is well known `that trinitro-cellulose or gun-cotton is explosive at a higher temperature, and is therefore less dangerous, than dinitro-cellulose, which is the soluble ber forming the basis of the various compounds of celluloid. In dehydrating the latter various methods havebeen proposed. In one instance the pulp has been placed in a closed vessel containing a suitable absorbent packed in bags, the particles of pulp being free to move in the vessel and come into close proximity to the absorbent or the bags containing the same. The vessel is then rotated until the maximum quantity of moisture has been abstracted-from the pulp. inasmuch, however, as it has been found necessary to employ very heavy hydraulic pressure to expel part of the water only from the pulp, it will be seen that the method referred to above cannot be relied upon to remove the requisite percentage of moisture unless a very considerable period of time and absorbents having a marked affinity for water are employed. In another instance the wet pulp has been molded into cakes or layers and built up in a pile of such cakes with alternate padsof bibulous paper. The pile thus formed is subjected to enormous hydraulic pressure, and the waterexpelled from the pulp is absorbed and retained by the bibulous pads lying between the cakes. This ods of dehydrating cellulose which involve a y sufficient degree of pressure to expel the proper amount of water are unavoidably dangerous by reason of the liability to explosion, which will always exist in a greater or less degree.

In other processes of manipulation cold air has been employed from which the moisture has been removed, the air being driven into and through the pulp or through a dryingroom containing it. Heated air has also been used in a similar manner, the pulp being treated while in a wet state, in combination with a liquid solvent, until it is reduced to a semi-liquid state.. It has also been proposed to grind the pyroxyline-pulp, mixing in at the same time camphor and such pigments or coloring materials as may be desired. After grinding, the pulp, still impregnated with water, is formed into cakes, and each cake, laid between bibulous pads, is placed upon a metallic sheet, a pile of such cakes being formed upon the press-bed'. To eifect the desiccation by this method, the pressure exerted is about seven thousand live hundred pounds to the square inch, the pile being exposed to such pressure for a time varying from forty minutes to one hour. The danger from explosion in this method is the same as that already mentioned, save that it is enhanced by the increased degree of pressure exerted.

Another method proposed is to place the nitrated and washed pulp in asuitable recepdissimilar tothe processes long employed in pharmacies and laboratories, depending upon IOO an aqueous displacement in this manner, the;

best results merely dividing the residuum ot" water at eaeh repetition ot the operation and increasing the proportion ol alcohol remaining in the pulp.

lt is well ascertained that' nitro-eellulose or pyroxyiine in a loose state and while in a damp or moist condition, and even when containing only thirty per rent. ot water, cannot be ignited or exploded by any ordinary methods. Even when it Contains the same pereent age of alcohol it is equally sale, sinee il' it. be ignited it will burn with a steady alcoholic llame, consuming the nit r11-cellulose, but withf ont danger ol explosion. ln this loose damp state it-is praetiealiy sal'e i'or handling in large quantities.

My invention contemplates the utilization i ot' these facts; and it Consists in the novel prof cess hereinafter fully described, and de tin itel v E pointed out in the elaims.

In carrying my invention into elteet I ein* ploy apparatus, one suitable form ot whieh is shown in the aeeompanying drawings, in wl1ioh- Figure l isa perspective view of the eoutainingwessel employed, the view showing the parts composing said vessel separated from l rubber strips 2li are vplat-ed in the meeting each other. Fig. 2 is a perspective view ol' a press adapted to the praetiee ot my invention. Fig. 3 is a horizontal seetion of Fig. l. taken in the line il 3l. seetion ol the entire apparatus.

l designates what lterm the containing or It is composed oli' y I'our walls, 2, iuclosng a rectangular spaee, z

" )ul i-reeeiviue vessel.

two of said walls being to the other two walls.

separably Connected position b v means ol a metallic re-enl'oreingband, 1v,whieh embraees the upper end of the container. At the lower end the four ver tical walls are supported by a 111etallie band, 5, having a flange, t5, turned at a right angle to the plane ot` the wall above and having its inner edge projecting within the inner surl`aee ol` the wall ol said container. 'lhe lower band, 5, is permanently l'astened to the vertieal walls ol' one-hal tf ol' the eontainer by means ol rivets or serews 7. (Seen in Fig. l.) The container is made ot' wood lined with Zine to reduce its weight; but other material may be used, it` preferred.

At the upper end 1 these walls are supported in proper relative l The walls are gained at Fig. l is a central vertical topand bottom to bringthe re-enl'orcing bands flush with the outer surfaces.

lVithin the container or reeeptaele l is placed a Afalse bottom, it, eomposed of any suitable material-sueh as wood or metal and provided with numerous eseape-openings, lt), t'ormed in the talse bottom itself, as well as with ehannels l2, t'ormed between the edges of the Yfalse bottom ..r and the inner surface ot' the vertical wall-piects 2, This false bottom is vertieallv movable within the eontainer l and rests normally upon the flange ti, formed by turning in tl11.1 low1'a r edges ol' the re-enM tforeing plates or bauds Upon any suitable l'orm ol' l'rame, l2), I mount a press-table having a plate, ll, upon which the base ol' the container may rest. 'lhs plate hasa tlange, l-t, inelosing a recess, 15, with which a discharge-pipe, ttl, communieates, said pipe having a coek, li', Beneath this skeleton tabhl is arranged the cylinder lla oliI a hydraulic press, said cylinder having a plunger, la, optnated in the well-known manner. This plunger is arranged to rise and lall through the skeleton table or base il and against the l'alse bottom tl, whieh is eonstructed to move 11p and down in the container l,

l'pon the press-table ll is mounted the press-box 20, which consists ol a rectangular structure, l, two ol.l the walls being rigidly mounted upon the n'ess-table, surrounding the flange il thereol', while the other two walls, 2l, are hinged to therigd walls. Upon the exterior ol' these walls are t'ormed or mounted ribs 22, having projeetng ends 23, whieh meet when thel press-box is closed and reeeive bolts` f-t and lever-nuts 25, whereby the joints may be tightly elosed. To make them air-t ight, or as nearly so as luactieable,

edges and engage with grooves 27 in the oorrespondingI edges ol` the hinged seetion 2l.

'.lhe press-box is terminated above by a )ross-head or strone dia )hraem 24s' having i 1 h n 7 i a ln the said drawlngs the reterenee-numeral openings ;.t, which lead into a close ehamber, 30, above. This ehaimber may, il.l desired, be divided by partitions il having top and bottoni openings iii. A diseharge-pipe, Sli, enters said ehambe'r ,i ust above the lloorthereol', and eonnnunicating with the top thereof are two pipes, fit and 35, the t'ormer leading to an' air-eonil'iressor, 3G, ol' any suitable construetion, and the latter to an aleohol-reservoir,37. Cocks 38 are plaeed in said pipes, and a similar shut-oil', 259, is placed in the pipe 33, which may Conveniently be earried down to and into the discharge-pipe lli.

lVith apparatus ol' this construction the mode ot' proeed 11 re is as follows: l take p vroxyline as it eomes Yt'rom the washing-tanks and place it in a eentrifugal extractor, which is operated until the pulp contains its own weight oll water. I then divide it,` into lots ol' about two pounds each, eaeh lot Containing one pound ot water. I now spread upon the TOO IOS

perforated false bottom 9 a sheet of muslin, upon which is spread the first lot of wet pulp. A second strip offabric is then spread upon the top of the pulp, and a second lot of pulp is laid upon the second piece of muslin. This arrangement is repeat-ed until the container is filled, each superimposed layer being-compacted as it is laid in place. The container now closed and placed in the press-box, and the door of the latter is closed tight. Being supported upon the press-table 14, the ram 19 of the hydraulic press rests against the false bottom of the container, and, the press being operated, the ram rises, carrying the false bottom with it and pressing the pulp between the latter and the diaphragm 2S. A comparatively light pressure will answer the purpose at this stage, four hundred pounds to the square inch giving excellent results, and with :l slowly-moving ram being entirely free from danger. Any suitable form of safety valve or gage may be attached to the pump of the press to open at the pressure indicated. The pulp is allowed to remain under pressure tor a short time or until the expelled water has tiowed out through the outlets required. When the operation is conducted as set forth, the pyroxyline will, while in the container and under pressure, part with thirty per cent. of the absorbed or adherent water, leaving seventy per cent. of the original bulk still remaining in the pulp. The valve 39 of the upper outlet, 33, is now closed and air is driven through the pipe 34 from the air pump or compressor. Entering the compacted pulp at the top it penetrates down through the same, driving off. the expressed water, which has not already escaped, into the chamber l5 and opening the spaces or cells in the pulp, which are filled with unexpressed aqueous particles, thereby leaving the material in excellent condition for the ensuing steps. The currents of air, also driven through the closely-compacted mass under pressure, carry off an additional quantity of the contained water, amounting to twenty per cent. of the entire amount, thereby le( ving in the mass about one-half of the original bulk. After the water ceases to flow the air is still for a further brief period driven through the pyroxyline, after which the airvalve is closed and the tap in pipe 35 is opened, admitting alcohol to the chamber 30, whence it drips through the diaphragm 28 and enters the pulp. Knowing the approximate quantity of water still remaining in the latter, the reservoir y37, with which the pipe 35 connects, is supplied with a quantity of alcohol greater by a few pounds than the amount of retained water, and the recess 15 is emptied of the water expressed by the ram and by the air. A vessel, 40, is placed upon a suitable scale, 4l., and brought under t-he lower outlet, Y16, the weight of the scale being set so that the beam shall tip when the water known to be in the pyroxyline shall have been received in the vessel. An electric or other call, 42,

may be arranged to operate bythe movement of the scale-beam to call the operators attention thereto, electric contacts 4S and il being placed on the scale-beam and scale-arm, respectively. The alcohol entering the container at the top penetrates down through the pyroxyline, driving before it the retained fifty per cent. ot' water, which passes oft' through the chamber l5 into the vessel upon the scale. The alcohol sinks into and passes through. the mass of pyroxyline by gravity, and by reason of its own dierent specific gravity it iloats or rests upon the contained water, driving it down before it it sinks through the compressed mass. About one hour, more or less, will be required for the completion of this stage o'l the alcohol treatment. Then the scale-beam rises, showing that the quantity ot' water estimated to remain in the pyroxyline after the treatment by compressed air has been received in the vessel upon the scale, this vessel is removed and at the same time the valve in the alcohol-pipe is closed and the compressed-air valve opened. The vessel removed from the scale is replaced by another to receive any hyd ated alcohol which may come away forfuture redistillation, and air is again blown through the pyroxyline until it retains from forty to fifty per cent. only of alcohol. The valve is now closed, the ram is run down, the press is opened, and the contents of the container are removed to zinclined boxes having' tight covers. The pyroxyline in the container will be found in thin layers easily separable by means of the interposed muslin. The quantity of camphor necessary to complete the conversion of the pyroxyline is now placed between the layers, which are piled one above another, and coloring-matter and pigments are added. The boxes containing the material are then tightly covered and set one side for the operation of the rolls, which completes the conversion of the pyroxyline into celluloid and other similar compounds.

By this process l secure several advantages, one of which is the rapid dehydration of the pyroxyline, enabling the manufacturer to treat a large quantity in a single day and with comparatively small expense. Again, the solvents are distributed through the pyroxyline so evenly and every particle thereof is so thoroughly saturated with the alcohol as to greatly promote and facilitate the subsequent operations attending the treatment by solvents. The dehydration of the pulp also is accomplished without danger, the pressure to which it is subjected being very light and the pulp being at all times in a moist condition. Finally, the process is speedy, simple, safe, and economical, the alcohol used being recovered by distillation, save as to that portion retained in the pulp and afterward combined with camphor. A

Vhile I have mentioned alcohol only, l may use any act-ive or non-active solvent in place thereof-such as amyl or chloride of amylas well as other well-known solvents.

lOO

The container l may be formed of any inaterial; but for lightness and economy wood lined with zinc may be employed. I may, however, use vulcanized rubber or metal and make the container of lany size. In practice I have usually construettal it` with a depth of thirty inches and a diameter of ten inches eaeh way, giving an interior space ot three thousand cuhie inches. I use these proportions because l have found that dinitro-cellulose, when closely compact ed, occupies a space equal to ninety-six eubie inches foreach pound avoirdupois ot' the pulp, and that when conipressed at the maximum pressure of fourhundred pounds to the square inch it occupies less than hall'the space named, or about iorty cubic inches. lhus a container olf the dimensions speci tied would be adapted to a charge ot about thirty pounds ol pyroxyliue in its hydrated condition that is to say, with an additional weight ot adherent or absorbed water about equal in weight to the weight of the pyroxyline.

\\"hat l claim isl. The process sel l'orth torthe dehydration ot dinitro-eellulose or pyroxyline, the same consisting in tirst subjecting the washed pulp to pressure, and then while still under pressure blowing air through the same, substantially as described.

L. 'lhe process herein set forth for the dehydration of dinit ro-cellulose and similar compounds, the same consisting in tirst exposing' the pulp to light` pressure to remove the excess ot water, then forcing air through the compacted mass, and then admitting alcohol to the upper end ot' the eontaini11g-vessel and allowing` ity to percolate through the pulp by gravity, subst antially as described.

3. The process set forth for the dehydration of dinitro-cellulose, consisting in first exposing the pulp to a light pressure, then foreing air through the compacted mass, then while still under pressure percolating alcohol through the pulp by gravity, and nally blowing air through the same to expel the surplus of alcohol, substantiallyY as described.

f-L. The process set forth for the dehydration of dinitro-cellulose, the same consisting in arranging the pulp in layers with interposed strips of fabric, subjecting it to a comparatively light pressure to expel the excess of water, then torciug air downward through the com paeted mass, then while still under pressure pereolatiugalcohol down through the pulp h v gravity, and tinally blowing air through the same to ren'love the excess of alcohol, sul)- st antially as described.

The process set l'orth l'or dehydrating dinitrocellulose, the same consisting in arranging the pulp, at'ter nitration and washing, in successive layers with interposed strips ot' tahrie, subjecting' it to lightl pressure, then i'oreing air down through the compacted pulp, then pereolating alcohol through the same by gravity, then blowing compressed air down through it to remove the excess of alcohol, separating the layers, and tinally placing eamphor with colta-ing-matter and pigments bctween the compressed layers, substantially as described.

In testimony whereol" l al'lix my signature in presence of two witnesses.

\\'t nesses:

Eow. S. FuLLiau, (motion (Y liLmo'r'r. 

